CN102828251A - Method for preparing aluminum nitride single crystal material - Google Patents
Method for preparing aluminum nitride single crystal material Download PDFInfo
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- CN102828251A CN102828251A CN2012103326526A CN201210332652A CN102828251A CN 102828251 A CN102828251 A CN 102828251A CN 2012103326526 A CN2012103326526 A CN 2012103326526A CN 201210332652 A CN201210332652 A CN 201210332652A CN 102828251 A CN102828251 A CN 102828251A
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Abstract
The invention relates to a method for preparing an aluminum nitride single crystal material, comprising the following steps: preparing a III-nitride nucleation layer on a substrate; preparing a III-nitride crystallization layer on the III-nitride nucleation layer; preparing a stress covariation layer on the III-nitride crystallization layer; preparing a III-nitride self-decomposing decoupling layer on the stress covariation layer; preparing a first III-nitride template layer on the III-nitride self-decomposing decoupling layer; preparing a second III-nitride template layer on the first III-nitride template layer; preparing an aluminum nitride thick-film monocrystalline material layer on the second III-nitride template layer; and preparing an aluminum nitride single crystal wafer substrate material by adopting an intermediate process. The method can be used for providing low-cost large-size aluminum nitride single crystal wafer substrate material to study and produce ultraviolet and deep-ultraviolet semiconductor optoelectronic devices, thereby having very good practical value and marketing prospect.
Description
Technical field
The present invention relates to a kind of semiconductor single crystal material preparation method, specifically is a kind of aluminum-nitride single crystal material preparation method.
Background technology
Along with third generation semiconductor gallium nitride (GaN) material is promoted in the photoelectric device extensive applications, greatly promote the research and development of ultra semiconductor material with wide forbidden band aluminium nitride AlN (AlN).Japanese NTT company developed first AlN base deep ultraviolet (wavelength 210nm) photodiode (LED) since 2006, became the new research focus of semiconductor applications based on the short wavelength's ultraviolet and the DUV electrical part of AlN and high Al component AlGaN material.But as adopt similar GaN base photoelectric device to utilize foreign substrate (like sapphire, silit and silicon) extension preparation method; Because needed growth temperature higher (at least 1300 ℃), the lattice mismatch that is born, thermal stresses and surface and interface problem will be more outstanding.Optimal mode is to adopt the AlN monocrystal material to carry out the photoelectric device preparation as homo-substrate, so just can effectively eliminate the big mismatch problems of AlN and high Al component AlGaN base device and develop high performance device.Therefore, AlN monocrystal material technology of preparing becomes the research focus that the semiconductor material preparation field is new in recent years.The AlN monocrystal material has using value of crucial importance and considerable economic benefit.
At present, the preparation technology commonly used who is used for the AlN monocrystal material has three kinds: metal-organic chemical vapor deposition equipment (MOCVD), halogenide vapour phase epitaxy (HVPE), physical vapor transmission (PVT).The relative merits of three kinds of technologies are following:
(1) MOCVD technology: be the mode that adopts chemosynthesis; Utilize metallic aluminium organic cpds (like TMAl) as the aluminium source; Ammonia (NH3) carries out the synthetic preparation of AlN thin-film material as nitrogenous source on foreign substrate such as high temperature (1200-1600 ℃) sapphire, silit.Its advantage is: 1) can prepare large-area AlN film monocrystal material.Area is by the size decision of foreign substrate and growth room, and maximum area can reach 6 inches of diameters at present; 2) can preparing growth, to obtain various meticulous mismatch stress adjusted and controlled and have a very even curface.This and the MOCVD process materials speed of growth are more closely related.Its shortcoming is: 1) be difficult to overcome high density dislocation (109-10/cm2), rete bending and be full of cracks problem that stress that hetero epitaxy produces causes.The thick more problem of the big more rete of area is outstanding more; 2) the MOCVD process materials speed of growth slow (per hour hundreds of nanometer thickness).Be not suitable for preparing the commercialization AlN single crystalline substrate material of hundreds of micron thick.
(2) HVPE technology: also be the mode that adopts chemosynthesis; Utilize metallic aluminium halogenide (like AlCl or AlCl3) as the aluminium source; Ammonia (NH3) carries out the synthetic preparation of AlN thick-film material as nitrogenous source on foreign substrate such as high temperature (1200-1600 ℃) sapphire, silit.Its advantage is: 1) also can prepare big area AlN monocrystal material.Also by the decision of foreign substrate and growth room's size, maximum area still has only 2 inches diameter to area at present; 2) the HVPE speed of growth is very fast, can prepare the AlN thick film monocrystal material that uses as substrate (tens and even hundreds of micron thick), and can better suppress the increment (dislocation desity 106-7/cm2) of break-through dislocation.Its shortcoming is: 1) be difficult to direct heteroepitaxial growth and obtain surfacing and have the higher crystalline quality materials.Often needing the AlN film monocrystal material of MOCVD prepared is the template of nucleation crystalline growth.Owing to need two equipment, cause the material produce cost high; 2) more difficultly overcome the crooked and be full of cracks problem of rete that stress that hetero epitaxy produces causes.Cause being difficult to peeling off from the heterojunction substrate and obtain complete large-area no supporting al N thick film monocrystal material, the big more rete of area is thick more outstanding more, and the finished material rate is low to be not suitable for commercialization and to promote.
(3) PVT technology: the mode that is the condensation of employing physical evaporation goes out the atmosphere of Al and N with high-purity AlN powder stock high temperature (1900-2400 ℃) physical evaporation, again condensation growing AIN body monocrystal material on the seed crystal with certain temperature gradient.Its advantage is: 1) material fast growth (per hour hundreds of micron thick).If any large size AlN seed crystal can prepare low-dislocation-density (102-4/cm2) but commercialization large size AlN body monocrystal material; 2) equipment construction and maintenance cost are low.Be very easy to large-scale production behind the technical maturity.Its shortcoming is: 1) no seed crystal prepares polycrystalline or the big grain material (crystal particle scale mm-scale or littler) of being easy to get of growing.Need be that seed crystal enlarges long brilliant size by the no supporting al N thick film monocrystal material of MOCVD and two kinds of technologies combinations of HVPE preparation; 2) material growth temperature very high (1900-2400 ℃) has requirements at the higher level to the material of growth room and structure and thermograde control.Although it is close that the energy consumption of PVT prepared growing AIN body monocrystalline and present sapphire body monocrystal material prepare, because its economic benefit considerable (every 2 inches AlN single-chip prices are more than 5,000 dollars at present) is expected with value and market outlook in fact most.
Summary of the invention
The objective of the invention is to conventional MOCVD, HVPE, PVT technology in the technical deficiency aspect the preparation aluminum-nitride single crystal material, aluminum-nitride single crystal material preparation method a kind of not only practical but also that can reduce cost is provided.
The present invention provides a kind of aluminum-nitride single crystal material preparation method, it is characterized in that, comprises following steps:
Step 1 a: substrate is inserted in the growth room of metal-organic chemical vapor deposition equipment-halogenide vapour phase epitaxy recombining process equipment;
Step 2: adopt mocvd process, preparation one III group-III nitride nucleating layer on substrate;
Step 3: substrate heating temperature is heated up, adopt mocvd process, preparation one III group-III nitride crystallizing layer on III group-III nitride nucleating layer;
Step 4: change the Heating temperature of substrate, adopt mocvd process, preparation one stress covariant layer on III group-III nitride crystallizing layer;
Step 5: adopt mocvd process, change the Heating temperature of substrate, preparation one III group-III nitride self-decomposition de layer on stress covariant layer;
Step 6: adopt mocvd process, change the Heating temperature of substrate, preparation one the one III group-III nitride template layer on III group-III nitride self-decomposition de layer;
Step 7: the Heating temperature of substrate is heated up, and the indium component in the III group-III nitride self-decomposition de layer raises with temperature and separates out, and between a stress covariant layer and an III group-III nitride template layer, forms porous loose structure;
Step 8: adopt mocvd process, substrate heating temperature is heated up, preparation one the 2nd III group-III nitride template layer on an III group-III nitride template layer;
Step 9: substrate heating temperature is heated up, adopt the halogenide process for vapor phase epitaxy, preparation one aluminium nitride AlN thick film monocrystalline material layer on the 2nd III group-III nitride template layer;
Step 10: substrate heating temperature is dropped to room temperature with 5 to 50 ℃/minute rate of temperature fall; Realization aluminium nitride AlN thick film monocrystal material is peeled off from substrate certainly, and in metal-organic chemical vapor deposition equipment-halogenide vapour phase epitaxy recombining process equipment growth room, takes out the thick film monocrystalline material layer;
Step 11: aluminium nitride AlN thick film monocrystalline material layer is inserted the top of the indoor tungsten crucible of the body monocrystalline material growth of physical vapor transmission equipment as seed crystal, high-purity aluminium nitride powder is inserted in the indoor tungsten crucible of the body monocrystalline material growth of physical vapor transmission equipment as raw material;
Step 12: the indoor Heating temperature of physical vapor transmission equipment body monocrystalline material growth is warmed up to 1900 to 2400 ℃; Through heating the thermograde regulation and control of warm area up and down; Keep the seed crystal warm area of the aluminium nitride AlN thick film monocrystal material of tungsten crucible top to be lower than 30 to 100 ℃ of the inner aluminum nitride powder powder stock of tungsten crucible warm areas; Adopting physical vapor transmission technology, is that seed crystal prepares growing aluminum nitride body monocrystal material with the thick film monocrystalline material layer;
Step 13: the body monocrystalline material growth chamber Heating temperature of physical vapor transmission equipment is dropped to room temperature take out the aluminum nitride body monocrystal material, prepare aluminum-nitride single crystal sheet substrate material through cutting, grind, polishing.
Utilization of the present invention is integrated in MOCVD and two kinds of technologies of HVPE the MOCVD-HVPE recombining process of same reaction chamber; The transition metal IVB group-III nitride stress covariant layer that has appropriate crystal lattice constant and a thermal expansivity through designing and preparing overcomes the stress that hetero epitaxy produces and causes the crooked and be full of cracks problem of rete; Particularly thermal expansivity is combined with the III group-III nitride self-decomposition de layer that comprises the indium component than heterogeneous single crystalline substrate and all big transition metal IVB group-III nitride stress covariant layer of aluminium nitride AlN; Can realize that prepared aluminium nitride AlN thick film monocrystal material is complete from peeling off on the heterogeneous single crystalline substrate, and then the big area seed crystal is provided for follow-up PVT technology enlarges aluminum nitride body single crystal growing size.The present invention can provide low-cost large size aluminum-nitride single crystal sheet substrate material for development and production ultraviolet and deep ultraviolet semiconductor photoelectric device, has extraordinary practical value and marketing prospect.
Description of drawings
For further specifying concrete technology contents of the present invention, below in conjunction with embodiment and accompanying drawing specifies as after, wherein:
Fig. 1 adopts the MOCVD-HVPE recombining process to prepare aluminium nitride AlN thick film monocrystal material structural representation.
Embodiment
See also shown in Figure 1ly, the present invention provides a kind of aluminum-nitride single crystal material preparation method, it is characterized in that, comprises following steps:
Step 1 a: substrate 1 is inserted in the growth room of metal-organic chemical vapor deposition equipment-halogenide vapour phase epitaxy recombining process equipment; Described substrate 1 is the heterogeneous single crystalline substrate of HMP, and its fusing point is higher than 1300 ℃ and with aluminium nitride AlN sapphire, silit or the gallium nitride material of good lattice match relation are arranged;
Step 2: adopt mocvd process, preparation one III group-III nitride nucleating layer 2 on substrate 1, described III group-III nitride nucleating layer 2 is GaN, AlN or AlGaN material, and preparation temperature is 300 to 700 ℃, and thickness is 5 to 500nm;
Step 3: substrate 1 Heating temperature is heated up; Adopt mocvd process; Preparation one III group-III nitride crystallizing layer 3 on III group-III nitride nucleating layer 2; Described III group-III nitride crystallizing layer 3 is GaN, AlN or AlGaN material, and the Heating temperature of substrate 1 rises to 900 to 1200 ℃, and the thickness of III group-III nitride crystallizing layer 3 is 10 to 1000nm;
Step 4: the Heating temperature that changes substrate 1; Adopt mocvd process; Preparation one stress covariant layer 4 on III group-III nitride crystallizing layer 3 is used for coordinating follow-up nitride template layer or the aluminium nitride AlN thick-film material prepares lattice mismatch stress and the thermal stresses that process produces.Described stress covariant layer 4 is transition metal IVB group-III nitride stress covariant layers; Its material is TiN, ZrN, HfN, TiZrN, TiHfN, ZrHfN or TiZrHfN; Its thermal expansivity will be higher than HMP single crystalline substrate 1 and aluminium nitride AlN; The Heating temperature that changes substrate 1 is 300 to 700 ℃ of low temperature, and the thickness of stress covariant layer 4 is 10 to 1000nm;
Step 5: adopt mocvd process; Change the Heating temperature of substrate 1; Preparation one III group-III nitride self-decomposition de layer 5 on stress covariant layer 4; Be used for auxiliary stress covariant layer 4 follow-up nitride template layer of coordination or aluminium nitride AlN thick-film material and prepare lattice mismatch stress and the thermal stresses that process produces, and from substrate 1, peel off certainly at material growth ending temperature-fall period and stress covariant layer 4 acting in conjunction impelling aluminium nitride AlN thick film.The material of described III group-III nitride self-decomposition de layer 5 is In
xGa
1-xN, In
xAl
1-xN or In
xAl
yGa
1-x-yN, its indium component x is 0.05 to 0.9, and the Heating temperature to 300 that changes substrate 1 during preparation is to 700 ℃, and the thickness of III group-III nitride self-decomposition de layer 5 is 5 to 500nm;
Step 6: adopt mocvd process; Change the Heating temperature of substrate 1; Preparation one III group-III nitride template layer 6 on III group-III nitride self-decomposition de layer 5; The material of a described III group-III nitride template layer 6 is GaN, AlN or AlGaN, and the Heating temperature to 300 that changes substrate during preparation is to 700 ℃, and an III group-III nitride template layer 6 thickness are 5 to 500nm;
Step 7: the Heating temperature of substrate 1 is heated up, and the indium component in the III group-III nitride self-decomposition de layer 5 raises with temperature and separates out, and between a stress covariant layer 4 and an III group-III nitride low temperature template layer 6, forms porous loose structure;
Step 8: adopt mocvd process; Substrate 1 Heating temperature is heated up; Preparation one the 2nd III group-III nitride template layer 7 on an III group-III nitride template layer 6; The material of described the 2nd III group-III nitride high temperature template layer 7 is GaN, AlN or AlGaN, and intensification back substrate Heating temperature is 900 to 1200 ℃, and the 2nd III group-III nitride high temperature template layer 7 thickness are 200 to 2000nm;
Step 9: substrate 1 Heating temperature is heated up, adopt the halogenide process for vapor phase epitaxy, preparation one aluminium nitride AlN thick film monocrystalline material layer 8 on the 2nd III group-III nitride template layer 7;
Step 10: substrate 1 Heating temperature is dropped to room temperature with 5 to 50 ℃/minute rate of temperature fall.Because it is all big with aluminium nitride AlN that the thermal expansivity of stress covariant layer 4 is compared substrate 1; The thermal stresses that temperature-fall period produces discharges transferring to earlier in the stress covariant layer 4; Because of above it being the porous loose structure of III group-III nitride; The two acting in conjunction has just realized that aluminium nitride AlN thick film monocrystal material 8 is complete from peeling off from the substrate 1 in the joint portion of power covariant layer 4 and porous loose structure.In metal-organic chemical vapor deposition equipment-halogenide vapour phase epitaxy recombining process equipment growth room, take out nothing support aluminium nitride AlN thick film monocrystalline material layer 8;
Step 11: aluminium nitride AlN thick film monocrystalline material layer 8 is inserted the top of the indoor tungsten crucible of the body monocrystalline material growth of physical vapor transmission equipment as seed crystal, high-purity aluminium nitride powder is inserted in the indoor tungsten crucible of the body monocrystalline material growth of physical vapor transmission equipment as raw material;
Step 12: the indoor Heating temperature of physical vapor transmission equipment body monocrystalline material growth is warmed up to 1900 to 2400 ℃; Through heating the thermograde regulation and control of warm area up and down; Keep the seed crystal warm area of the aluminium nitride AlN thick film monocrystal material of tungsten crucible top to be lower than 30 to 100 ℃ of the inner aluminum nitride powder powder stock of tungsten crucible warm areas; Adopting physical vapor transmission technology, is that seed crystal prepares growing aluminum nitride body monocrystal material with aluminium nitride AlN thick film monocrystalline material layer 8;
Step 13: the body monocrystalline material growth chamber Heating temperature of physical vapor transmission equipment is dropped to room temperature take out the aluminum nitride body monocrystal material, prepare aluminum-nitride single crystal sheet substrate material through cutting, grind, polishing.
Above-mentioned semiconductor single crystal material preparation method can provide low-cost large size low-dislocation-density aluminum-nitride single crystal sheet substrate material for development and production ultraviolet and deep ultraviolet semiconductor photoelectric device.
A kind of aluminum-nitride single crystal material preparation method of the present invention is compared existing conventional aluminum-nitride single crystal material method.Have following characteristics and beneficial effect:
(1) adopts the MOCVD-HVPE recombining process; The transition metal IVB group-III nitride stress covariant layer that has appropriate crystal lattice constant and a thermal expansivity through designing and preparing overcomes the crooked and be full of cracks problem of film forming layer that stress that hetero epitaxy produces is made; Particularly thermal expansivity is combined than all big transition metal IVB group-III nitride stress covariant layer of heterogeneous single crystalline substrate and aluminium nitride AlN and the III group-III nitride self-decomposition de layer that comprises the indium component porous loose structure that is decomposed to form that heats up, can realize that prepared aluminium nitride AlN thick film monocrystal material is complete from peeling off and then obtain unsupported aluminium nitride AlN thick film monocrystal material on the heterogeneous single crystalline substrate;
(2) big area of utilizing the MOCVD-HVPE recombining process to prepare does not have the aluminium nitride AlN of support thick film monocrystal material and is seed crystal; Can enlarge the size and raising material growth quality of PVT process high-temperature growing aluminum nitride body monocrystal material, and then be that follow-up large size aluminum nitride body monocrystal material PVT process scale preparation production lays the foundation.
(3) technological merit with MOCVD, HVPE, three kinds of technologies of PVT organically combines, and not only greatly reduces aluminum-nitride single crystal material prepn production cost, also is easy to large-scale production.
Introduce the above-mentioned aluminum-nitride single crystal material preparation method of preparation below.Should be appreciated that the preparation method who below describes is merely the specific examples of preparation aluminum-nitride single crystal material of the present invention.Those skilled in the art can reach other factors as required and make change under the present invention instruct.
Embodiment 1:
Adopt sapphire (a-Al2O3) material following as the technical process that heterogeneous single crystalline substrate prepares aluminium nitride AlN (AlN) thick film monocrystal material and aluminium nitride AlN (AlN) body monocrystal material:
Step 1: with the a-Al of 2 inches diameter
2O
3Single crystalline substrate material 1 is inserted in the growth room of MOCVD-HVPE recombining process equipment;
Step 2: adopt golden MOCVD technology, with 550 ℃ substrate heating temperature, low temperature prepares the thick GaN low temperature of 30nm nucleating layer 2 on the sapphire single-crystal substrate material;
Step 3: substrate heating temperature is risen to 1050 ℃, adopt MOCVD technology, high temperature prepares the thick GaN high temperature crystallization of 500nm layer 3 on GaN low temperature nucleating layer 2;
Step 4: substrate heating temperature is reduced to 600 ℃, adopt MOCVD technology, low temperature prepares the thick TiN stress of 50nm covariant layer 4 on GaN high temperature crystallization layer 3;
Step 5: adopt MOCVD technology, with 600 ℃ substrate heating temperature, low temperature prepares the In of the thick indium component of 30nm x=0.15 on TiN stress covariant layer 4
0.15Ga
0.85N self-decomposition de layer 5;
Step 6: adopt MOCVD technology, with 600 ℃ substrate heating temperature, at In
0.15Ga
0.85Low temperature prepares the thick GaN low temperature template layer 6 of a 100nm on the N self-decomposition de layer 5;
Step 7: substrate heating temperature slowly is warming up to 1050 ℃ of high temperature, In with 10 ℃/minute temperature rise rate
0.15Ga
0.85Indium component in the N self-decomposition de layer 5 raises with temperature and separates out, and between TiN thermal stresses covariant layer 4 and GaN low temperature template layer 6, forms the porous loose structure of GaN;
Step 8: adopt MOCVD technology, with 1050 ℃ substrate heating temperature, the GaN high temperature template layer 7 of preparation one thick 1000nm on GaN low temperature template layer 6;
Step 9: substrate heating temperature is risen to 1350 ℃, adopt HVPE technology, high temperature prepares the thick AlN thick film of one 100 μ m monocrystal material 8 on GaN high temperature template layer 7;
Step 10: substrate heating temperature is dropped to room temperature with 30 ℃/minute rate of temperature fall, realize that AlN thick film monocrystal material 8 is from a-Al
2O
3Certainly peel off on the substrate 1, and in MOCVD-HVPE recombining process equipment growth room, take out no supporting al N thick film monocrystal material 8.
Step 11: AlN thick film monocrystal material 8 is inserted the top of the indoor tungsten crucible of the body monocrystalline material growth of PVT equipment as seed crystal, high-purity AlN powder is inserted in the indoor tungsten crucible of the body monocrystalline material growth of PVT equipment as raw material;
Step 12: the indoor Heating temperature of PVT device body monocrystalline material growth is heated to 2350 ℃; Through heating the thermograde regulation and control of warm area up and down; Keep the seed crystal warm area of the AlN thick film monocrystal material of tungsten crucible top to be lower than 70 ℃ of the inner AlN powder stock of tungsten crucible warm areas; Adopting PVT technology, is the thick AlN body of seed crystal high temperature preparation growth 10mm monocrystal material with AlN thick film monocrystal material;
Step 13: the body monocrystalline material growth chamber Heating temperature of PVT equipment is dropped to room temperature take out AlN body monocrystal material, prepare AlN single-chip substrate material through cutting, grind, polishing.
Adopt silit (6H-SiC) material following as the technical process that heterogeneous single crystalline substrate prepares aluminium nitride AlN (AlN) thick film monocrystal material and AlN body monocrystal material:
Step 1: 2 inches diameter 300 micron thick 6H-SiC single crystalline substrate materials 1 are inserted in the growth room of MOCVD-HVPE recombining process equipment;
Step 2: adopt MOCVD technology, with 650 ℃ substrate heating temperature, low temperature prepares the thick AlN low temperature of 20nm nucleating layer 2 on 6H-SiC single crystalline substrate material;
Step 3: substrate heating temperature is risen to 1300 ℃, adopt MOCVD technology high temperature on AlN low temperature nucleating layer 2 to prepare the thick AlN high temperature crystallization of 300nm layer 3;
Step 4: substrate heating temperature is reduced to 650 ℃, adopt MOCVD technology, low temperature prepares the thick HfN stress of 50nm covariant layer 4 on AlN high temperature crystallization layer 3;
Step 5: adopt MOCVD technology, with 650 ℃ substrate heating temperature, low temperature prepares the In of the thick indium component of 20nm x=0.25 on HfN stress covariant layer 4
0.25Al
0.75N self-decomposition de layer 5;
Step 6: adopt MOCVD technology, with 650 ℃ substrate heating temperature, at In
0.25Al
0.75Low temperature prepares the thick AlGaN low temperature template layer 6 of a 50nm on the N self-decomposition de layer 5;
Step 7: substrate heating temperature slowly is warming up to 1300 ℃ of high temperature, In with 15 ℃/minute temperature rise rate
0.25Al
0.75Indium component in the N self-decomposition de layer 5 raises with temperature and separates out, and between HfN stress covariant layer 4 and AlGaN low temperature template layer 6, forms the porous loose structure of AlN;
Step 8: adopt MOCVD technology, with 1300 ℃ substrate heating temperature, the AlN high temperature template layer 7 of preparation one thick 1500nm on AlGaN low temperature template layer 6;
Step 9: substrate heating temperature is risen to 1450 ℃, adopt HVPE technology high temperature on AlN high temperature template layer 7 to prepare the thick AlN thick film of one 200 μ m monocrystal material 8;
Step 10: substrate heating temperature is dropped to room temperature with 50 ℃/minute rate of temperature fall, realize AlN thick film monocrystal material 8 from the 6H-SiC substrate 1 from peeling off, and in MOCVD-HVPE recombining process equipment growth room, take out no supporting al N thick film monocrystal material 8.
Step 11: AlN thick film monocrystal material 8 is inserted the top of the indoor tungsten crucible of the body monocrystalline material growth of PVT equipment as seed crystal, high-purity AlN powder is inserted in the indoor tungsten crucible of the body monocrystalline material growth of PVT equipment as raw material;
Step 12: the indoor Heating temperature of PVT device body monocrystalline material growth is heated to 2300 ℃; Through heating the thermograde regulation and control of warm area up and down; Keep the seed crystal warm area of the AlN thick film monocrystal material of tungsten crucible top to be lower than 60 ℃ of the inner AlN powder stock of tungsten crucible warm areas; Adopting PVT technology, is the thick AlN body of seed crystal high temperature preparation growth 20mm monocrystal material with AlN thick film monocrystal material;
Step 13: the body monocrystalline material growth chamber Heating temperature of PVT equipment is dropped to room temperature take out AlN body monocrystal material, prepare AlN single-chip substrate material through cutting, grind, polishing.
Adopt gan (GaN) material following as the technical process that heterogeneous single crystalline substrate prepares aluminium nitride AlN thick film monocrystal material and aluminum nitride body monocrystal material:
Step 1: the GaN single crystalline substrate material 1 of 2 inches diameter 200 micron thick is inserted in the growth room of MOCVD-HVPE vapour phase epitaxy recombining process equipment;
Step 2: adopt MOCVD technology, with 550 ℃ substrate heating temperature, low temperature prepares the thick ZrN stress of 50nm covariant layer 4 on the GaN single crystalline substrate material 1;
Step 5: adopt MOCVD technology, with 550 ℃ substrate heating temperature, low temperature prepares the In of the thick In component of 30nm x=0.3 on ZrN thermal stresses covariant layer 4
0.3Ga
0.7N self-decomposition de layer 5;
Step 6: adopt MOCVD technology, with 550 ℃ substrate heating temperature, at In
0.3Ga
0.7Low temperature prepares the thick GaN low temperature of 50nm template layer 6 on the N self-decomposition de layer 5;
Step 7: substrate heating temperature slowly is warming up to 1100 ℃ of high temperature, In with 20 ℃/minute temperature rise rate
0.3Ga
0.7In component in the N self-decomposition de layer 5 raises with temperature and separates out, and between ZrN stress covariant layer 4 and GaN low temperature template layer 6, forms the porous loose structure of GaN;
Step 8: adopt MOCVD technology, with 1100 ℃ substrate heating temperature, the GaN high temperature template layer 7 of preparation one thick 500nm on GaN low temperature template layer 6;
Step 9: substrate heating temperature is risen to 1500 ℃, adopt HVPE technology, high temperature prepares the thick AlN thick film of one 300 μ m monocrystal material 8 on GaN high temperature template layer 7;
Step 10: substrate heating temperature is dropped to room temperature with 25 ℃/minute rate of temperature fall, realize AlN thick film monocrystal material 8 from the GaN substrate 1 from peeling off, and in MOCVD-HVPE recombining process equipment growth room, take out no supporting al N thick film monocrystal material 8.
Step 11: AlN thick film monocrystal material 8 is inserted the top of the indoor tungsten crucible of the body monocrystalline material growth of PVT equipment as seed crystal, high-purity AlN powder is inserted in the indoor tungsten crucible of the body monocrystalline material growth of PVT equipment as raw material;
Step 12: the indoor Heating temperature of PVT device body monocrystalline material growth is heated to 2250 ℃; Through heating the thermograde regulation and control of warm area up and down; Keep the seed crystal warm area of the AlN thick film monocrystal material of tungsten crucible top to be lower than 50 ℃ of the inner AlN powder stock of tungsten crucible warm areas; Adopting PVT technology, is the thick AlN body of seed crystal high temperature preparation growth 30mm monocrystal material with AlN thick film monocrystal material;
Step 13: the body monocrystalline material growth chamber Heating temperature of PVT equipment is dropped to room temperature take out AlN body monocrystal material, prepare AlN single-chip substrate material through cutting, grind, polishing.
What should explain at last is, above example is only in order to technical scheme of the present invention to be described but not limit it.Although with reference to given example the present invention is specified, those of ordinary skill in the art can make amendment to technical scheme of the present invention as required or be equal to replacement, and does not break away from the spirit and the scope of technical scheme of the present invention.
Claims (8)
1. an aluminum-nitride single crystal material preparation method is characterized in that, comprises following steps:
Step 1 a: substrate is inserted in the growth room of metal-organic chemical vapor deposition equipment-halogenide vapour phase epitaxy recombining process equipment;
Step 2: adopt mocvd process, preparation one III group-III nitride nucleating layer on substrate;
Step 3: substrate heating temperature is heated up, adopt mocvd process, preparation one III group-III nitride crystallizing layer on III group-III nitride nucleating layer;
Step 4: change the Heating temperature of substrate, adopt mocvd process, preparation one stress covariant layer on III group-III nitride crystallizing layer;
Step 5: adopt mocvd process, change the Heating temperature of substrate, preparation one III group-III nitride self-decomposition de layer on stress covariant layer;
Step 6: adopt mocvd process, change the Heating temperature of substrate, preparation one the one III group-III nitride template layer on III group-III nitride self-decomposition de layer;
Step 7: the Heating temperature of substrate is heated up, and the indium component in the III group-III nitride self-decomposition de layer raises with temperature and separates out, and between a stress covariant layer and an III group-III nitride template layer, forms porous loose structure;
Step 8: adopt mocvd process, substrate heating temperature is heated up, preparation one the 2nd III group-III nitride template layer on an III group-III nitride template layer;
Step 9: substrate heating temperature is heated up, adopt the halogenide process for vapor phase epitaxy, preparation one aluminium nitride AlN thick film monocrystalline material layer on the 2nd III group-III nitride template layer;
Step 10: substrate heating temperature is dropped to room temperature with 5 to 50 ℃/minute rate of temperature fall; Realization aluminium nitride AlN thick film monocrystal material is peeled off from substrate certainly, and in metal-organic chemical vapor deposition equipment-halogenide vapour phase epitaxy recombining process equipment growth room, takes out the thick film monocrystalline material layer;
Step 11: aluminium nitride AlN thick film monocrystalline material layer is inserted the top of the indoor tungsten crucible of the body monocrystalline material growth of physical vapor transmission equipment as seed crystal, high-purity aluminium nitride powder is inserted in the indoor tungsten crucible of the body monocrystalline material growth of physical vapor transmission equipment as raw material;
Step 12: the indoor Heating temperature of physical vapor transmission equipment body monocrystalline material growth is warmed up to 1900 to 2400 ℃; Through heating the thermograde regulation and control of warm area up and down; Keep the seed crystal warm area of the aluminium nitride AlN thick film monocrystal material of tungsten crucible top to be lower than 30 to 100 ℃ of the inner aluminum nitride powder powder stock of tungsten crucible warm areas; Adopting physical vapor transmission technology, is that seed crystal prepares growing aluminum nitride body monocrystal material with the thick film monocrystalline material layer;
Step 13: the body monocrystalline material growth chamber Heating temperature of physical vapor transmission equipment is dropped to room temperature take out the aluminum nitride body monocrystal material, prepare aluminum-nitride single crystal sheet substrate material through cutting, grind, polishing.
2. aluminum-nitride single crystal material preparation method according to claim 1; Wherein the substrate described in the step 1 is the heterogeneous single crystalline substrate of HMP, and its fusing point is higher than 1300 ℃ and with aluminium nitride AlN sapphire, silit or the gallium nitride material of good lattice match relation are arranged.
3. aluminum-nitride single crystal material preparation method according to claim 1, wherein the III group-III nitride nucleating layer described in the step 2 is GaN, AlN or AlGaN material, and preparation process substrate heating temperature is 300 to 700 ℃, and thickness is 5 to 500nm.
4. aluminum-nitride single crystal material preparation method according to claim 1; Wherein the III group-III nitride crystallizing layer described in the step 3 is GaN, AlN or AlGaN material; The Heating temperature of substrate rises to 900 to 1200 ℃, and the thickness of III group-III nitride crystallizing layer is 10 to 1000nm.
5. aluminum-nitride single crystal material preparation method according to claim 1; Wherein the stress covariant layer described in the step 4 is a transition metal IVB group-III nitride stress covariant layer; Its material is TiN, ZrN, HfN, TiZrN, TiHfN, ZrHfN or TiZrHfN; Its thermal expansivity is higher than HMP single crystalline substrate and aluminium nitride AlN, and the Heating temperature that changes substrate is 300 to 700 ℃, and the thickness of stress covariant layer is 10 to 1000nm.
6. aluminum-nitride single crystal material preparation method according to claim 1, wherein the material of the III group-III nitride self-decomposition de layer described in the step 5 is In
xGa
1-xN, In
xAl
1-xN or In
xAl
yGa
1-x-yN, its indium component x is 0.05 to 0.9, and the Heating temperature to 300 that changes substrate during preparation is to 700 ℃, and the thickness of III group-III nitride self-decomposition de layer is 5 to 500nm.
7. aluminum-nitride single crystal material preparation method according to claim 1; Wherein the material of the III group-III nitride template layer described in the step 6 is GaN, AlN or AlGaN; The Heating temperature to 300 that changes substrate during preparation is to 700 ℃, and an III group-III nitride template layer thickness is 5 to 500nm.
8. aluminum-nitride single crystal material preparation method according to claim 1; Wherein the material of the 2nd III group-III nitride template layer described in the step 8 is GaN, AlN or AlGaN; Substrate heating temperature is warming up to 900 to 1200 ℃, and the 2nd III group-III nitride template layer thickness is 200 to 2000nm.
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